EP0712848B1 - Process of preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphth-2-amides, in high purity for the preparation of azodyes - Google Patents
Process of preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphth-2-amides, in high purity for the preparation of azodyes Download PDFInfo
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- EP0712848B1 EP0712848B1 EP95117130A EP95117130A EP0712848B1 EP 0712848 B1 EP0712848 B1 EP 0712848B1 EP 95117130 A EP95117130 A EP 95117130A EP 95117130 A EP95117130 A EP 95117130A EP 0712848 B1 EP0712848 B1 EP 0712848B1
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- hydroxy
- naphthoic acid
- aminobenzimidazolone
- benzimidazolon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
Definitions
- the invention relates to a process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide in high for azo pigments required purity by converting 3-hydroxy-2-naphthoic acid into Toluene or xylene with thionyl chloride and subsequent condensation with 5-aminobenzimidazolone in N-methylpyrrolidone in the presence of Sodium.
- 3-Hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide is an important one Intermediate product for the production of high-fast azo pigments.
- 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide can be prepared in 84% yield by reaction of excess 3-hydroxy-2-naphthoic acid and 5-aminobenzimidazolone in xylene with phosphorus trichloride ( DD 265894).
- a disadvantage of this process is that the excess 3-hydroxy-2-naphthoic acid has to be recovered again, which makes the process economically unfavorable. Both processes result in a wastewater containing phosphorus.
- This object is achieved by a process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide, starting from 5-aminobenzimidazolone and 3-hydroxy-2-naphthoic acid chloride, characterized in that 5-aminobenzimidazolone and sodium carbonate in N-methylpyrrolidone and one Solution of 3-hydroxy-2-naphthoic acid chloride in xylene or toluene metered in within at least 2 hours, filtered, washed with xylene, the filter cake in water with sodium carbonate is added, enters and steam distilled, sucks off the residue, washes and dries.
- 3-Hydroxy-2-naphthoic acid chloride is made from 1 mol 3-Hydroxy-2-naphthoic acid in approx. 5 parts by volume of xylene or toluene per part of 3-hydroxy-2-naphthoic acid by reaction with 1.05 thionyl chloride under Adding a catalyst, such as. B. N, N'-dimethylformamide, pyridine, Triethylamine, made at 47-50 ° C. The solution thus prepared continues reacted with 5-aminobenzimidazolone.
- a catalyst such as. B. N, N'-dimethylformamide, pyridine, Triethylamine
- 5-aminobenzimidazolone is used in an amount of 0.9 to 1 mol, in particular 0.95 mol per mol of 3-hydroxy-2-naphthoic acid.
- Sodium carbonate is used in an amount of 0.8 to 1.8, especially 1.0 to 1.3 mol per mol of 3-hydroxy-2-naphthoic acid used.
- N-methylpyrrolidone is in 3 to 6, in particular 4 to 5 parts by volume per part of 5-aminobenzimidazolone, used.
- reaction of the solution of 3-hydroxy-2-naphthoic acid chloride in xylene or Toluene with 5-aminobenzimidazolone is at 15 to 40, especially 20 to 35 ° C.
- the dosing time of the 3-hydroxy-2-naphthoic acid chloride is important for the purity of the resulting product.
- the metering time should be at least 2 h, in particular 4 h, preferably between 4 and 10 h. It is also possible to choose a longer addition time than 10 h, but there is no advantage in terms of purity.
- 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide can be produced in 85% yield and in the very high purity required for the production of high-fast azo pigments. A further cleaning, as in the prior art, can be omitted.
- 2500 ml of water are placed in a 6 l four-necked flask with stirrer, internal thermometer and distillation bridge with a 1 l single-necked flask as a template. Then the filter cake is entered. 200.0 g of sodium carbonate are then added and the mixture is heated to 100.degree. Xylene and water distill off.
- the product is suctioned off at 100 ° C. and the filter cake is washed several times with a total of 6250 ml of water until neutral.
- the product thus obtained is unusable for the production of high-fastness Azo pigments and according to HPLC contains approx. 0.1% 5-aminobenzimidazolone, approx. 0.8% 3-hydroxy-2-naphthoic acid and is also contaminated.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid in hoher für Azopigmente erforderlicher Reinheit durch Umsetzung von 3-Hydroxy-2-naphthoesäure in Toluol bzw. Xylol mit Thionylchlorid und anschließender Kondensation mit 5-Aminobenzimidazolon in N-Methylpyrrolidon in Anwesenheit von Natriumcarbonat.The invention relates to a process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide in high for azo pigments required purity by converting 3-hydroxy-2-naphthoic acid into Toluene or xylene with thionyl chloride and subsequent condensation with 5-aminobenzimidazolone in N-methylpyrrolidone in the presence of Sodium.
3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid ist ein wichtiges Zwischenprodukt für die Herstellung von hochechten Azopigmenten.3-Hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide is an important one Intermediate product for the production of high-fast azo pigments.
Es ist bekannt, daß man 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid
durch Umsetzung von 3-Hydroxy-2-naphthoesäure und 5-Aminobenzimidazolon
in N-Methylpyrrolidon mit Phosphortrichlorid bei
Temperaturen von 105-150°C in 84 % Ausbeute in einer gelben Modifikation,
die für Azopigmente tauglich ist, herstellen kann (DE 2758818). Ebenso ist
bekannt, daß man 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid
durch Reaktion von stark überschüssiger 3-Hydroxy-2-naphthoesäure und 5-Aminobenzimidazolon
in Xylol mit Phosphortrichlorid in 84 % Ausbeute
herstellen kann (DD 265894). Nachteilig an diesem Verfahren ist, daß die
überschüssige 3-Hydroxy-2-naphthoesäure wieder zurückgewonnen werden
muß, wodurch das Verfahren ökonomisch ungünstig wird. Bei beiden Verfahren
entsteht ein phosphorhaltiges Abwasser.
In der CS 178560 wird die Umsetzung von einer Lösung von 3-Hydroxy-2-naphthoesäurechlorid
in Toluol mit 5-Aminobenimidazolon in der 30 fachen
Menge Wasser in Anwesenheit von Natriumacetat zu 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid
in 86 % Ausbeute beschrieben.
Nachteilig an diesem Verfahren sind die großen Reaktionsvolumina.It is known that 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide by reacting 3-hydroxy-2-naphthoic acid and 5-aminobenzimidazolone in N-methylpyrrolidone with phosphorus trichloride at temperatures of 105-150 ° C can produce in 84% yield in a yellow modification which is suitable for azo pigments (DE 2758818). It is also known that 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide can be prepared in 84% yield by reaction of excess 3-hydroxy-2-naphthoic acid and 5-aminobenzimidazolone in xylene with phosphorus trichloride ( DD 265894). A disadvantage of this process is that the excess 3-hydroxy-2-naphthoic acid has to be recovered again, which makes the process economically unfavorable. Both processes result in a wastewater containing phosphorus.
In CS 178560 the reaction of a solution of 3-hydroxy-2-naphthoic acid chloride in toluene with 5-aminobenimidazolone in 30 times the amount of water in the presence of sodium acetate to 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid-2 -amide described in 86% yield. The large reaction volumes are disadvantageous in this process.
Die Umsetzung von stöchiometrischen Mengen 3-Hydroxy-2-naphthoesäurechlorid und 5-Aminobenzimidazolen in organischen Säuren in Gegenwart der Natrium- oder Kaliumsalze dieser Säuren (Polnische P 119895) ist bekannt. Eine Verbesserung dieser Herstellungsmethode besteht im Ersatz der organischen Säuren durch N,N'-Dimethylformamid bzw. N-Methylpyrrolidon (Polnische P 144734 und Dyes and Pigments 12, 57-63 (1990)). Das nach dieser Herstellmethode hergestellte 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid entspricht nicht den Anforderungen für Azopigmente, da das Produkt noch zuviel Ausgangsmaterial enthält (siehe Vergleichsbeispiel 1). Ein weiterer Nachteil dieses Verfahrens sind die langen Saugzeiten bei der Isolation des Produktes (siehe Vergleichsbeispiel 1.)The implementation of stoichiometric amounts of 3-hydroxy-2-naphthoic acid chloride and 5-aminobenzimidazoles in organic acids in Presence of the sodium or potassium salts of these acids (Polish P 119895) is known. An improvement of this manufacturing method is the replacement the organic acids by N, N'-dimethylformamide or N-methylpyrrolidone (Polish P 144734 and Dyes and Pigments 12, 57-63 (1990)). That after 3-Hydroxy-N-benzimidazolon-5-yl-naphthoic acid-2-amide produced by this production method does not meet the requirements for azo pigments because the product still contains too much starting material (see comparative example 1). Another disadvantage of this process is the long suction times during the Isolation of the product (see comparative example 1.)
Bei den meisten obengenannten Verfahren entsteht 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid nicht in der erforderlichen hohen Reinheit für Azopigmente. Deshalb müssen diese Produkte für die Herstellung hochechter Azopigmente, wie in der DE 2758818 beschrieben, über das Alkalisalz gereinigt werden.Most of the above-mentioned processes produce 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide not in the required high Purity for azo pigments. That is why these products need to be manufactured high-fast azo pigments, as described in DE 2758818, via the Alkali salt can be cleaned.
Es bestand daher ein Bedürfnis nach einem wirtschaftlichen und technisch leicht durchführbaren Verfahren zur Herstellung von 3-Hydroxy-N-benzimidazolon-5-yl-napthoesäure-2-amid in einer sehr hohen Reinheit für die Herstellung von hochechten Azopigmenten.There was therefore a need for an economical and technically easy feasible process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-napthoic acid-2-amide in a very high purity for the production of high-fast azo pigments.
Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung von 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid, ausgehend von 5-Aminobenzimidazolon und 3-Hydroxy-2-naphthoesäurechlorid, dadurch gekennzeichnet, daß man 5-Aminobenzimidazolon und Natriumcarbonat in N-Methylpyrrolidon vorlegt und eine Lösung von 3-Hydroxy-2-naphthoesäurechlorid in Xylol oder Toluol innerhalb von mindestens 2 Stunden zudosiert, filtriert, mit Xylol wäscht, den Filterkuchen in Wasser, das mit Natriumcarbonat versetzt ist, einträgt und wasserdampfdestilliert, den Rückstand absaugt, wäscht und trocknet. This object is achieved by a process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide, starting from 5-aminobenzimidazolone and 3-hydroxy-2-naphthoic acid chloride, characterized in that 5-aminobenzimidazolone and sodium carbonate in N-methylpyrrolidone and one Solution of 3-hydroxy-2-naphthoic acid chloride in xylene or toluene metered in within at least 2 hours, filtered, washed with xylene, the filter cake in water with sodium carbonate is added, enters and steam distilled, sucks off the residue, washes and dries.
3-Hydroxy-2-naphthoesäurechlorid wird nach an sich bekannter Weise aus 1 mol 3-Hydroxy-2-naphthoesäure in ca. 5 Volumenteilen Xylol bzw. Toluol pro Teil 3-Hydroxy-2-naphthoesäure durch Umsetzung mit 1,05 Thionylchlorid unter Zusatz eines Katalysators, wie z. B. N,N'-Dimethylformamid, Pyridin, Triethylamin, bei 47-50°C hergestellt. Die so hergestellte Lösung wird weiter mit 5-Aminobenzimidazolon umgesetzt.3-Hydroxy-2-naphthoic acid chloride is made from 1 mol 3-Hydroxy-2-naphthoic acid in approx. 5 parts by volume of xylene or toluene per part of 3-hydroxy-2-naphthoic acid by reaction with 1.05 thionyl chloride under Adding a catalyst, such as. B. N, N'-dimethylformamide, pyridine, Triethylamine, made at 47-50 ° C. The solution thus prepared continues reacted with 5-aminobenzimidazolone.
Üblicherweise verfährt man bei der Herstellung von 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid so, daß man 5-Aminobenzimidazolon und Natriumcarbonat in N-Methylpyrrolidon vorlegt und eine Lösung von 3-Hydroxy-2-naphthoesäurechlorid in Xylol bzw. Toluol in 4 bis 10 h zudosiert. Anschließend wird filtriert, mit Xylol bzw. Toluol gewaschen und der Filterkuchen in Wasser eingetragen, mit Natriumcarbonat versetzt und destilliert. Es wird erneut abgesaugt, der Filterkuchen vorzugsweise mit Wasser neutral gewaschen und getrocknet.The usual procedure for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide so that you can 5-aminobenzimidazolone and sodium carbonate in N-methylpyrrolidone and a solution of 3-hydroxy-2-naphthoic acid chloride added in xylene or toluene in 4 to 10 h. It is then filtered, washed with xylene or toluene and the Filter cake added to water, mixed with sodium carbonate and distilled. It is suctioned off again, the filter cake preferably neutral with water washed and dried.
5-Aminobenzimidazolon wird in einer Menge von 0,9 bis 1 mol, insbesondere 0,95 mol pro mol 3-Hydroxy-2-naphthoesäure, eingesetzt.5-aminobenzimidazolone is used in an amount of 0.9 to 1 mol, in particular 0.95 mol per mol of 3-hydroxy-2-naphthoic acid.
Natriumcarbonat wird in einer Menge von 0,8 bis 1,8, insbesondere 1,0 bis 1,3 mol pro mol 3-Hydroxy-2-naphthoesäure, eingesetzt.Sodium carbonate is used in an amount of 0.8 to 1.8, especially 1.0 to 1.3 mol per mol of 3-hydroxy-2-naphthoic acid used.
N-Methylpyrrolidon wird in 3 bis 6, insbesondere 4 bis 5 Volumenteilen je Teil 5-Aminobenzimidazolon, verwendet.N-methylpyrrolidone is in 3 to 6, in particular 4 to 5 parts by volume per part of 5-aminobenzimidazolone, used.
Die Reaktion der Lösung von 3-Hydroxy-2-naphthoesäurechlorid in Xylol bzw. Toluol mit 5-Aminobenzimidazolon wird bei 15 bis 40, insbesondere 20 bis 35°C, durchgeführt.The reaction of the solution of 3-hydroxy-2-naphthoic acid chloride in xylene or Toluene with 5-aminobenzimidazolone is at 15 to 40, especially 20 to 35 ° C.
Die Wasserdampfdestillation wird vorteilhaft mit 5 bis 7 Teilen Wasser und 0,5 bis 0,6 Teilen Natriumcarbonat je Teil 5-Aminobenzimidazolon durchgeführt. Steam distillation is advantageous with 5 to 7 parts of water and 0.5 to 0.6 parts of sodium carbonate per part of 5-aminobenzimidazolone performed.
Durch die Wasserdampfdestillation gelingt es überraschenderweise, die Verunreinigungen abzutrennen, so daß der Rückstand nach Absaugen und Waschen mit Wasser sehr reines Zielprodukt darstellt.Steam distillation surprisingly succeeds in that Separate impurities so that the residue after suction and Washing with water represents a very pure target product.
Die Dosierzeit des 3-Hydroxy-2-naphthoesäurechlorides ist für die Reinheit des
entstehenden Produktes von Bedeutung. Um 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid
in der erforderlichen Pigmentreinheit zu erhalten, sollte
die Dosierzeit mindestens 2 h, insbesondere 4 h, bevorzugt zwischen 4 und
10 h betragen. Es ist auch möglich, eine längere Zugabezeit als 10 h zu wählen,
jedoch ist damit kein Vorteil bezüglich der Reinheit vorhanden.
Nach dem obengenannten Verfahren kann 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid
in 85 % Ausbeute und in sehr hoher Reinheit, die für die
Herstellung von hochechten Azopigmenten erforderlich ist, hergestellt werden.
Eine weitere Reinigung, wie nach dem Stand der Technik, kann entfallen.The dosing time of the 3-hydroxy-2-naphthoic acid chloride is important for the purity of the resulting product. In order to obtain 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide in the required pigment purity, the metering time should be at least 2 h, in particular 4 h, preferably between 4 and 10 h. It is also possible to choose a longer addition time than 10 h, but there is no advantage in terms of purity.
According to the above-mentioned process, 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide can be produced in 85% yield and in the very high purity required for the production of high-fast azo pigments. A further cleaning, as in the prior art, can be omitted.
In einem 2l-Vierhalskolben mit Innenthermometer, Gasableitungsrohr und Rührer werden 494,0 g (2,63 mol) 3-Hydroxy-2-napthoesäure und 2470,0 g = 2872 ml Xylol vorgelegt, mit 6,0 g N,N'-Dimethylformamid versetzt, 328,0 g = 201,1 ml (2,76 mol) Thionylchlorid bei 47-50°C über 1 h zudosiert und bis zum Ende der Gasentwicklung 3 h nachgerührt. Man erhält 3181,8 g 3-Hydroxy-2-naphthoesäurechlorid in Xylol als klare Lösung.In a 2-liter four-necked flask with an internal thermometer, gas discharge pipe and stirrer 494.0 g (2.63 mol) of 3-hydroxy-2-naphthoic acid and 2470.0 g = 2872 ml of xylene submitted, mixed with 6.0 g of N, N'-dimethylformamide, 328.0 g = 201.1 ml (2.76 mol) of thionyl chloride were metered in at 47-50 ° C. over 1 h and until End of gas evolution stirred for 3 h. 3181.8 g of 3-hydroxy-2-naphthoic acid chloride are obtained in xylene as a clear solution.
In einem 10 l-Vierhalskolben mit Tropftrichter, Rückflußkühler,
Innenthermometer und Rührer werden 1750 ml N-Methylpyrrolidon vorgelegt.
Hierzu gibt man 291,5 g (2,75 mol) Natriumcarbonat. Danach werden bei ca.
25°C 372,5 g (2,5 mol) 5-Aminobenzimidazolon zugegeben. In die so erhaltene
Suspension werden unter Rühren 3181,8 g 3-Hydroxy-2-naphthoesäurechlorid
(aus 494,0 g (2,63 mol) 3-Hydroxy-2-naphthoesäure) in Xylol in 6,5 h bei 25-28°C
zudosiert. Nach beendeter Zugabe wird bei Raumtemperatur 30 min
nachgerührt. Das ausgefallene Produkt wird abgesaugt (Saugzeit: 50 min) und
der Filterkuchen in 10 Portionen mit insgesamt 2150,0 g = 2500 ml Xylol
gewaschen.
In einem 6 l-Vierhalskolben mit Rührer, Innenthermometer und
Destillationsbrücke mit einem 1 l-Einhalskolben als Vorlage werden 2500 ml
Wasser vorgelegt. Danach wird der Filterkuchen eingetragen. Anschließend wird
mit 200,0 g Natriumcarbonat versetzt und auf 100°C erhitzt. Es destillieren
Xylol und Wasser ab. Das Produkt wird bei 100°C abgesaugt und der
Nutschkuchen mehrmals mit insgesamt 6250 ml Wasser neutral gewaschen. Es
falllen 1571,4 g Naphtholon wasserfeucht an. Nach dem Trocknen des
Filterkuchens bei 100°C/100 Torr erhält man 681,7 g (2,135 mol) 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid,
dies entspricht einer Ausbeute
von 85,4 % d. Th. bezogen auf 5-Aminobenzimidazolon.
Das so erhaltene Produkt ist tauglich für die Herstellung von hochechten
Azopigmenten und enthält nach HPLC < 0,1 % 5-Aminobenzimidazolon und
< 0,1 % 3-Hydroxy-2-naphthoesäure.1750 ml of N-methylpyrrolidone are placed in a 10 l four-necked flask with a dropping funnel, reflux condenser, internal thermometer and stirrer. 291.5 g (2.75 mol) of sodium carbonate are added. Then 372.5 g (2.5 mol) of 5-aminobenzimidazolone are added at about 25 ° C. 3181.8 g of 3-hydroxy-2-naphthoic acid chloride (from 494.0 g (2.63 mol) of 3-hydroxy-2-naphthoic acid) in xylene are added to the suspension thus obtained in 6.5 hours at 25-28 ° C added. After the addition has ended, the mixture is stirred at room temperature for 30 min. The precipitated product is suctioned off (suction time: 50 min) and the filter cake is washed in 10 portions with a total of 2150.0 g = 2500 ml xylene.
2500 ml of water are placed in a 6 l four-necked flask with stirrer, internal thermometer and distillation bridge with a 1 l single-necked flask as a template. Then the filter cake is entered. 200.0 g of sodium carbonate are then added and the mixture is heated to 100.degree. Xylene and water distill off. The product is suctioned off at 100 ° C. and the filter cake is washed several times with a total of 6250 ml of water until neutral. 1571.4 g of naphtholone are obtained when they are wet with water. After drying the filter cake at 100 ° C / 100 torr, 681.7 g (2.135 mol) of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide are obtained, this corresponds to a yield of 85.4% of theory . Th. Based on 5-aminobenzimidazolone.
The product obtained in this way is suitable for the production of high-fast azo pigments and, according to HPLC, contains <0.1% 5-aminobenzimidazolone and <0.1% 3-hydroxy-2-naphthoic acid.
99,0 g (0,52 mol) 3-Hydroxy-2-naphthoesäure und 1 ml N,N'-Dimethylformamid werden in 600 ml Chlorbenzol vorgelegt und bei 40°C mit 68,5 g = 42 ml (0,58 mol) Thionylchlorid versetzt. Es wird 1,5 h bei 40°C nachgerührt und anschließend überschüssiges Thionylchlorid unter Vakuum abdestilliert. Es werden 776,8 g 3-Hydroxy-2-naphthoesäurechlorid in Chlorbenzol als klare Lösung erhalten.99.0 g (0.52 mol) of 3-hydroxy-2-naphthoic acid and 1 ml of N, N'-dimethylformamide are placed in 600 ml of chlorobenzene and at 40 ° C with 68.5 g = 42 ml (0.58 mol) thionyl chloride was added. The mixture is stirred at 40 ° C for 1.5 h and then excess thionyl chloride was distilled off under vacuum. It 776.8 g of 3-hydroxy-2-naphthoic acid chloride in chlorobenzene as clear Get solution.
75,0 g (0,5 mol) 5-Aminobenzimidazolon und 41 g wasserfreies Natriumacetat werden in 700 ml N,N'-Dimethylformamid vorgelegt und bei 5°C 776,8 g 3-Hydroxy-2-naphthoesäurechlorid (aus 99,0 g (0,52 mol) 3-Hydroxy-2-naphthoesäure) in Chlorbenzol bei 5-10°C in 30 min zudosiert. Nach beendeter Zugabe wurde 3 h bei 20°C nachgerührt, auf 50°C erwärmt und filtriert. Der Filterkuchen saugt schlecht ab (Saugzeit: 14 h). Zur Reinigung wird der Filterkuchen in 1 l Methanol aufgenommen verrührt, abgesaugt, mit 250 ml Methanol und anschließend mehrmals mit insgesamt 1 l siedendem Wasser gewaschen. Nach dem Trocknen werden 130,3 g 3-Hydroxy-N-benzimidazolon-5-yl-naphthoesäure-2-amid erhalten, dies entspricht 81,7 % d. Th.75.0 g (0.5 mol) of 5-aminobenzimidazolone and 41 g of anhydrous sodium acetate are placed in 700 ml of N, N'-dimethylformamide and at 5 ° C 776.8 g of 3-hydroxy-2-naphthoic acid chloride (from 99.0 g (0.52 mol) 3-hydroxy-2-naphthoic acid) metered in chlorobenzene at 5-10 ° C in 30 min. After finished The addition was stirred at 20 ° C. for 3 h, warmed to 50 ° C. and filtered. The Filter cake sucks off poorly (suction time: 14 h). For cleaning the Filter cake taken in 1 l of methanol, stirred, suction filtered, with 250 ml Methanol and then several times with a total of 1 liter of boiling water washed. After drying, 130.3 g of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide received, this corresponds to 81.7% of theory. Th.
Das so erhaltene Produkt ist unbrauchbar für die Herstellung von hochechten Azopigmenten und enthält nach HPLC ca. 0,1 % 5-Aminobenzimidazolon, ca. 0,8 % 3-Hydroxy-2-naphthoesäure und ist zusätzlich verunreinigt.The product thus obtained is unusable for the production of high-fastness Azo pigments and according to HPLC contains approx. 0.1% 5-aminobenzimidazolone, approx. 0.8% 3-hydroxy-2-naphthoic acid and is also contaminated.
Claims (7)
- A process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-2-naphthamide, starting from 5-aminobenzimidazolone and 3-hydroxy-2-naphthoyl chloride, which comprises initially introducing 5-aminobenzimidazolone and sodium carbonate in N-methylpyrrolidone and metering in a solution of 3-hydroxy-2-naphthoyl chloride in xylene or toluene over the course of at least 2 hours, filtering, washing with xylene or toluene, introducing the filter cake into water to which sodium carbonate has been added and steam-distilling, filtering off the residue with suction, washing and drying.
- The process as claimed in claim 1, wherein 5-aminobenzimidazolone is employed in an amount of from 0.9 to 1 mol, preferably 0.95 mol, per mole of 3-hydroxy-2-naphthoic acid.
- The process as claimed in claim 1 or 2, wherein sodium carbonate is employed in an amount of from 0.8 to 1.8, preferably 1.0 to 1.3, mol per mole of 3-hydroxy-2-naphthoic acid.
- The process as claimed in at least one of claims 1 to 3, wherein N-methylpyrrolidone is used in 3 to 6, preferably 4 to 5, parts by volume per part of 5-aminobenzimidazolone.
- The process as claimed in at least one of claims 1 to 4, wherein the reaction of the solution of 3-hydroxy-2-naphthoyl chloride in xylene or toluene with 5-aminobenzimidazolone is carried out at 15 to 40°C, preferably 20 to 35°C.
- The process as claimed in claim 5, wherein the addition time is at least 4 h, preferably 4 to 10 hours.
- The process as claimed in at least one of claims 1 to 6, wherein the steam distillation is carried out using 5 to 7 parts of water and 0.5 to 0.6 parts of sodium carbonate per part of 5-amino-benzimidazolone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4441146 | 1994-11-18 | ||
| DE4441146A DE4441146A1 (en) | 1994-11-18 | 1994-11-18 | Process for the preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphthoic acid 2-amide in high purity required for azo pigments |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0712848A2 EP0712848A2 (en) | 1996-05-22 |
| EP0712848A3 EP0712848A3 (en) | 1997-01-08 |
| EP0712848B1 true EP0712848B1 (en) | 2000-09-27 |
Family
ID=6533608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95117130A Expired - Lifetime EP0712848B1 (en) | 1994-11-18 | 1995-10-31 | Process of preparation of 3-hydroxy-N-benzimidazolon-5-yl-naphth-2-amides, in high purity for the preparation of azodyes |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5756757A (en) |
| EP (1) | EP0712848B1 (en) |
| JP (1) | JP3954121B2 (en) |
| BR (1) | BR9505216A (en) |
| DE (2) | DE4441146A1 (en) |
| DK (1) | DK0712848T3 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503970B1 (en) | 2000-09-29 | 2003-01-07 | Engelhard Corporation | Co-processed pigments |
| CN101838244B (en) * | 2010-06-03 | 2012-11-21 | 山东金城医药化工股份有限公司 | Organic solvent synthetic method of azoic coupling component ASBI |
| JP5612977B2 (en) * | 2010-09-17 | 2014-10-22 | エア・ウォーター株式会社 | Process for producing 6-bromo-N-methyl-2-naphthamide |
| CN102532035B (en) * | 2011-12-30 | 2014-01-15 | 郭祥荣 | Method for synthesizing azoic coupling component AS-BI |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2758818A1 (en) * | 1977-12-30 | 1979-07-12 | Hoechst Ag | NEW CRYSTAL MODIFICATION OF 5- (2'-HYDROXY-3'-NAPHTHOYL-AMINO) -BENZIMIDAZOLONE- (2), METHOD FOR MANUFACTURING AND USING IT |
| DD265894A1 (en) * | 1987-11-10 | 1989-03-15 | Bitterfeld Chemie | PROCESS FOR PREPARING 5- (3'-HYDROXYNAPHTHOYL-2'-AMINO) -BENZIMIDAZOLONE |
-
1994
- 1994-11-18 DE DE4441146A patent/DE4441146A1/en not_active Withdrawn
-
1995
- 1995-10-31 DE DE59508752T patent/DE59508752D1/en not_active Expired - Fee Related
- 1995-10-31 DK DK95117130T patent/DK0712848T3/en active
- 1995-10-31 EP EP95117130A patent/EP0712848B1/en not_active Expired - Lifetime
- 1995-11-16 US US08/559,551 patent/US5756757A/en not_active Expired - Fee Related
- 1995-11-16 JP JP29856895A patent/JP3954121B2/en not_active Expired - Fee Related
- 1995-11-17 BR BR9505216A patent/BR9505216A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0712848A3 (en) | 1997-01-08 |
| EP0712848A2 (en) | 1996-05-22 |
| JPH08225749A (en) | 1996-09-03 |
| BR9505216A (en) | 1997-09-16 |
| JP3954121B2 (en) | 2007-08-08 |
| DE4441146A1 (en) | 1996-05-23 |
| US5756757A (en) | 1998-05-26 |
| DE59508752D1 (en) | 2000-11-02 |
| DK0712848T3 (en) | 2000-10-30 |
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